CN112190761B - Carbon-based composite material artificial bone repair material and preparation method thereof - Google Patents

Carbon-based composite material artificial bone repair material and preparation method thereof Download PDF

Info

Publication number
CN112190761B
CN112190761B CN202011037042.4A CN202011037042A CN112190761B CN 112190761 B CN112190761 B CN 112190761B CN 202011037042 A CN202011037042 A CN 202011037042A CN 112190761 B CN112190761 B CN 112190761B
Authority
CN
China
Prior art keywords
carbon
layer
artificial bone
temperature
composite material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011037042.4A
Other languages
Chinese (zh)
Other versions
CN112190761A (en
Inventor
谭周建
张翔
王斌
刘波
蔡志霞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Carbon Kang Biotechnology Co ltd
Original Assignee
Hunan Carbon Kang Biotechnology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Carbon Kang Biotechnology Co ltd filed Critical Hunan Carbon Kang Biotechnology Co ltd
Priority to CN202011037042.4A priority Critical patent/CN112190761B/en
Publication of CN112190761A publication Critical patent/CN112190761A/en
Application granted granted Critical
Publication of CN112190761B publication Critical patent/CN112190761B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/08—Carbon ; Graphite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/10—Ceramics or glasses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention provides a carbon-based composite material artificial bone repair material and a preparation method thereof, the carbon-based composite material artificial bone repair material is characterized in that a ceramic layer and a pyrolytic carbon layer are sequentially arranged on the surface of a carbon-based porous material, a metal layer and a low-temperature carbon layer are sequentially generated on the surface of a carbon-based porous material substrate of a copying artificial bone, then high-temperature heat treatment is carried out to convert the metal layer and the low-temperature carbon layer into the ceramic layer, and the pyrolytic carbon layer is deposited, so that the artificial bone repair material which realizes bionics in shape and function is obtained.

Description

Carbon-based composite material artificial bone repair material and preparation method thereof
Technical Field
The invention relates to an artificial bone repairing material, in particular to a carbon-based composite material artificial bone repairing material and a preparation method thereof, belonging to the technical field of biological material preparation.
Background
Clinically, artificial bone implantation is an effective means for anatomically reconstructing clinical treatment due to bone defects caused by trauma, tumors, infection, and dysplasia. At present, the artificial bone implant materials mainly comprise metal, ceramic and high polymer materials, and the following problems mainly exist: the metal has the defects of easy abrasion, easy fatigue, easy corrosion, bone absorption, artifact of medical images and the like; the polymer material has the defects of poor aging and creep resistance, toxic reaction, thrombosis and the like, and the ceramic material has the defects of no plasticity, brittle quality, easy fracture and the like.
In recent years, the composite material with excellent mechanical property is rapidly developed, and a favorable opportunity is provided for the inorganic non-metallization of the artificial bone material. The carbon-based material has good biocompatibility, such as no medical image artifact, no toxic substance release, fiber reinforcement and the like, and shows the biomechanical property matched with the autogenous bone of a human body. For example, chinese patent (CN 108577957A) discloses a carbon/carbon-silicon carbide composite bone plate, which comprises a carbon/carbon composite base material formed by sequentially and alternately laminating 0 ° non-woven fabric, a carbon fiber mesh and 90 ° non-woven fabric, and the surface of the base material is coated with pyrolytic carbon and silicon carbide coatings. Chinese patent (CN 108171798A) discloses that a personalized carbon-ceramic composite material bone fracture plate is prepared by selective laser melting 3D printing according to a medical image data model, and the used chopped carbon fibers are distributed in the structure in a uniformly distributed or non-uniformly distributed mode, and the surface of the chopped carbon fibers is coated with resin carbon, so that anatomical reconstruction can be realized. In fact, the human bone is a compact cortical layer (with the hardness of 0.6 GPa-1.0 GPa) at the outer layer and a low-density cancellous bone at the center, and the artificial bone not only has the shape bionics, but also has the function bionics in the macroscopic structure, such as light weight, low heat conduction and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide an artificial bone repair material which realizes bionic on both form and function, the inner part of the artificial bone repair material is a carbon-based porous material substrate bionic low-density cancellous bone with high porosity, the heat conductivity coefficient can be effectively reduced, the low elastic modulus is ensured, the surface is compounded with a bionic cortical layer, a ceramic layer is used as a transition layer to provide the developing property and a blocking layer of the artificial bone profile, the influence caused by the falling off of particles to the outside due to mechanical damage of the carbon-based porous material substrate is prevented, the outer high-temperature pyrolysis carbon layer provides a smoother surface and a soft contact surface, and the frictional abrasion between a hard ceramic inner layer and the human autologous bone stump is avoided.
The second purpose of the invention is to provide a preparation method of the carbon-based composite material artificial bone repair material, which has simple operation and low cost and is beneficial to large-scale production.
In order to achieve the technical purpose, the invention provides a carbon-based composite material artificial bone repair material, which is characterized in that a ceramic layer and a pyrolytic carbon layer are sequentially arranged on the surface of a carbon-based porous material.
The carbon-based porous material of the substrate of the carbon-based composite material artificial bone repair material is a bionic low-density cancellous bone, has high porosity, can effectively reduce the heat conductivity coefficient, and ensures the low elastic modulus of the artificial bone, and the ceramic layer is a transition layer, so that the developability of the contour of the artificial bone can be improved, and the carbon-based composite material artificial bone repair material can be used as a blocking layer to prevent the porous substrate from causing the falling of particles and transferring the particles to the outside due to mechanical damage to bring adverse effects, such as the influence of particle foreign matters, the transfer along with tissues and the like. The external high-temperature pyrolytic carbon coating can provide a smoother surface and a soft contact surface, and the hard ceramic inner layer and the human autologous bone stump are prevented from being abraded due to friction.
As a preferable scheme, the carbon-based porous material is a carbon fiber/carbon composite material; the carbon fiber/carbon composite material is composed of a carbon fiber fabric formed by alternately laminating and needling a plurality of layers of carbon fiber cloth and carbon fiber nets or formed by laminating and needling a plurality of layers of single carbon fiber nets and a carbon matrix inside the carbon fiber fabric (the carbon matrix is distributed on the surfaces of the carbon fibers and filled among the carbon fibers).
Preferably, the porosity of the carbon fiber/carbon composite material is 40% to 60%. The carbon fiber/carbon composite material with higher porosity can effectively reduce the heat conductivity coefficient by being used as a matrix, and ensures lower elastic modulus of the artificial bone.
Preferably, the ceramic layer is formed by at least one of Ti, si, W, cr, ta and Zr and the low-temperature carbon layer at a high temperature of 1000-1500 ℃.
Preferably, the thickness of the ceramic layer is 3 μm to 15 μm. The thicker the ceramic layer, the lower the overall thermal conductivity of the composite coating, but the higher the surface hardness, and therefore needs to be controlled within a suitable thickness range.
Preferably, the pyrolytic carbon layer has a thickness of 5 to 50 μm. The thicker the pyrolytic carbon coating, the lower the overall surface hardness of the composite coating, but the greater its thermal conductivity. Accordingly, the cooperative control of the thicknesses of the ceramic layer and the pyrolytic carbon layer can ensure that the hardness and thermal conductivity of the composite coating are within appropriate ranges.
As a preferred scheme, the surface of the carbon-based composite material artificial bone repair material is provided with fixing holes and drainage holes, the hole diameter is 0.5 mm-5.0 mm, and the carbon-based composite material artificial bone repair material is mainly used for fixing the artificial bone repair material with human tissues or bones and the like.
The invention also provides a preparation method of the carbon-based composite material artificial bone repairing material, which comprises the steps of generating a metal layer on the surface of a carbon-based porous material substrate of the profiling artificial bone through magnetron sputtering in sequence, generating a low-temperature carbon layer through magnetron sputtering or plasma enhanced chemical vapor deposition, then carrying out high-temperature heat treatment to enable the metal layer and the low-temperature carbon layer to form a ceramic layer, and then carrying out chemical vapor deposition to pyrolyze the carbon layer to obtain the carbon-based composite material artificial bone repairing material.
As a preferred scheme, the metal layer is generated by magnetron sputtering under the following conditions: vacuum degree of 1X 10 -1 Pa～5×10 -1 Pa; the negative bias voltage of the workpiece is 50V-200V; the Ar flow is 20sccm to 200sccm; the purity of the metal target is not lower than 99wt%, and the power is 1 kW-3 kW; the revolution speed of the material table is 10 r/min-30 r/min; the deposition temperature is 200-400 ℃; the deposition time is 60 min-300 min; the metal target is at least one of Ti, si, W, cr, ta and Zr. The thickness of the metal layer is generally controlled to be in the range of 1 μm to 5 μm. The invention adopts a magnetron sputtering method to generate the metal layer, mainly based on that magnetron sputtering tends to deposit on the surface of the carbon-based porous material, and can effectively keep the high porosity of the carbon-based porous material.
Preferably, the thickness of the low temperature carbon layer is controlled to be in the range of 2 μm to 10 μm.
As a preferable embodiment, the low-temperature carbon layer is formed by magnetron sputtering under the following conditions: vacuum degree of 1X 10 -1 Pa～5×10 -1 Pa; the negative bias voltage of the workpiece is 10V-200V; the Ar flow is 50sccm to 120sccm; the power of the graphite target is 1 kW-3 kW; the purity of the graphite target is not lower than99.99wt%; the revolution speed of the material table is 10 r/min-30 r/min; the heating temperature is 80-200 ℃; the deposition time is 60min to 600min;
or the low-temperature carbon layer is generated by plasma enhanced chemical vapor deposition, and the generation conditions are as follows: vacuum degree of 1X 10 -1 Pa～5×10 -1 Pa; the negative bias voltage of the workpiece is 10V-200V; the Ar flow is 50sccm to 120sccm; the power of the ion source is 0.5 kW-5 kW; the flow rate of the hydrocarbon gas is 10sccm to 500sccm; the heating temperature is 80-300 ℃; the deposition time is 60min to 600min.
As a preferred embodiment, the chemical vapor deposition pyrolytic carbon layer is formed by chemical vapor deposition under the following conditions: adopting a gas carbon source, and depositing for 10-100 h at the temperature of 900-1500 ℃. The thickness of the pyrolytic low temperature carbon layer is generally controlled to be 5-50 μm.
Preferably, the carbon-based porous material matrix of the profiling artificial bone is formed by carbon fiber fabrics and carbon matrixes between the carbon fiber surfaces and the carbon fibers. The carbon fiber fabric is formed by compounding carbon fiber cloth and carbon fiber nets in a crossed, laminated and needled mode or is formed by compounding a plurality of layers of single carbon fiber nets in a laminated and needled mode, the thickness of the carbon fiber fabric is determined according to the thickness requirement of the artificial bone, and the shape of the carbon fiber fabric is also determined according to the actual requirement. Preferred carbon fiber cloth is 1k, 3k, 6k, 12k or 24k laid carbon fiber cloth. The preferred carbon fiber web has an areal density of 10g/m 2 ～60g/m 2 。
The invention provides a preparation method of artificial bone repair of a carbon-based composite material, which comprises the following specific steps:
1) According to the thickness required by artificial bone repair, carrying out cross lamination needling compounding on a plurality of layers of carbon fiber cloth and carbon fiber nets or adopting a plurality of layers of single carbon fiber net lamination needling compounding to the required thickness to obtain a carbon fiber preform, wherein the carbon fiber cloth is 1k, 3k, 6k, 12k or 24k non-weft carbon fiber cloth; the areal density of the carbon fiber web was 10g/m 2 ～60g/m 2 ；
2) Densifying the carbon fiber preform to obtain the matrix carbon, wherein the process of densifying the matrix carbon comprises chemical vapor deposition or/and impregnation-cracking:
the chemical vapor deposition process conditions are as follows: putting the carbon fiber preform into a deposition furnace, and introducing a carbon-containing gas source (natural gas, methane or propylene, and the like, nitrogen or hydrogen is used as diluent gas, and the flow ratio of the carbon source gas to the diluent gas is 1:0-2) at the temperature of 850-1300 ℃ to obtain a porous carbon-based composite material blank;
the impregnation-cracking process conditions are as follows: the carbon fiber preform is subjected to densification processes such as resin (furan, phenolic aldehyde, furfuryl ketone and the like) or asphalt (petroleum asphalt, coal asphalt) vacuum pressurization impregnation, curing treatment, cracking (resin: 900-1050 ℃, normal pressure; asphalt: 750-850 ℃, 50-200 MPa) and the like, wherein the impregnation pressure is 1.0-5.0 MPa, and the impregnation time is 2-10 h; the curing temperature is 160-230 ℃, and the curing time is 10-50 h; the cracking time is 2-20 h; obtaining a porous carbon-based composite material blank;
3) Putting the obtained blank into a high-temperature furnace, heating under the condition of vacuum or protective atmosphere to remove impurities, wherein the treatment temperature is 1500-2300 ℃, and the heat preservation time is 1-10 h, and the step can be optionally adopted or not adopted;
4) Processing the sheet blank into a copying artificial bone blank (comprising a preset hole) according to an artificial bone defect filling model designed according to medical image data (CT or MRI);
5) Sequentially depositing a metal layer and a low-temperature carbon layer on the surface of the artificial bone blank;
the metal layer is generated by magnetron sputtering, and the generation conditions are as follows: vacuum degree of 1X 10 -1 Pa～5×10 -1 Pa; the negative bias voltage of the workpiece is 50V-200V; the Ar flow is 20sccm to 200sccm; the purity of the metal target is not lower than 99wt%, and the power is 1 kW-5 kW; the revolution speed of the material table is 10 r/min-30 r/min; the deposition temperature is 200-400 ℃; the deposition time is 60min to 300min;
the low-temperature carbon layer is generated by magnetron sputtering, and the generation conditions are as follows: vacuum degree of 1X 10 -1 Pa～5×10 -1 Pa; the negative bias voltage of the workpiece is 10V-200V; ar flow is 50 sccm-120 sccm; the power of the graphite target is 1 kW-3 kW; the purity of the graphite target is not lower than 99.99wt%; the revolution speed of the material table is 10 r/min-30 r/min; the heating temperature is 80-200 ℃; the deposition time is 60min to 600min;
or the low-temperature carbon layer is generated by plasma enhanced chemical vapor deposition, and the generation conditions are as follows: vacuum degree of 1X 10 -1 Pa～5×10 -1 Pa; the negative bias voltage of the workpiece is 10V-200V; ar flow is 50 sccm-120 sccm; the power of the ion source is 0.5 kW-5 kW; the flow rate of the hydrocarbon gas is 10sccm to 500sccm; the heating temperature is 80-300 ℃; the deposition time is 60min to 600min; the hydrocarbon gas is common short-chain alkane, such as methane, ethane and the like;
6) Subjecting 5) to high temperature treatment (conditions: the temperature is 850-1300 ℃; the time is 1-3 h; vacuum or protective atmosphere Ar) to obtain a transition layer containing a ceramic phase;
7) Preparing a deposited pyrolytic carbon coating on the surface of the artificial bone blank body with the ceramic phase formed on the surface;
the pyrolytic carbon coating is generated by chemical vapor deposition, and the generation conditions are as follows: depositing a gas carbon source (such as natural gas, methane and other common gas carbon sources) at 900-1500 ℃ for 10-100 h.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1) The artificial bone repairing material disclosed by the invention is bionic in form and function and is closer to a human native bone structure, the shape of the artificial bone repairing material can be designed at will according to an artificial bone defect filling model designed according to medical image data (CT or MRI), functionally, the inner part of the artificial bone repairing material is a carbon-based porous material matrix bionic low-density cancellous bone with high porosity, the heat conductivity coefficient can be effectively reduced, the elastic modulus is ensured, the surface composite layer is a bionic cortical layer, the ceramic layer is used as a transition layer to provide the developing property and the blocking layer of the artificial bone profile, the influence caused by the falling and transferring of particles to the outside due to mechanical damage of the porous carbon matrix is prevented, the external high-temperature pyrolytic carbon layer provides a smoother surface and a soft contact surface, and the frictional wear of a hard ceramic inner layer and a self bone and the like is avoided. The elastic modulus of the artificial bone repairing material prepared by the technical scheme of the invention is 10 GPa-20 GPa, the surface hardness is 3 GPa-10 GPa, and the heat conductivity coefficient is less than 1 w/(m.K), so that the artificial bone repairing material is particularly suitable for repairing the defects of sternum and skull.
2) The artificial bone repairing material has simple preparation process and low cost, and is favorable for industrial production.
Drawings
FIG. 1 is a drawing of a sternum patch in substance;
the left image in fig. 2 is a scanning electron microscope image of a structure in which a metal layer and a low-temperature carbon layer are formed on the surface of a carbon-based porous material; the right picture is a scanning electron microscope picture of a ceramic layer and a pyrolytic carbon layer structure formed on the surface of the carbon-based porous material, and the coating shows that an obvious interface exists between the metal layer and the low-temperature carbon layer before high-temperature treatment, and the interface disappears after the high-temperature treatment to form a uniform ceramic phase.
Detailed Description
The following examples are intended to illustrate the present disclosure in further detail, but not to limit the scope of the claims.
Example 1
1) Multiple layers of carbon fiber cloth (6 k, 160g/m) 2 ) And carbon fiber mesh (60 g/m) 2 ) The cross laminated layer is needled and compounded to the required thickness to obtain the bulk density of 0.4g/cm 3 The carbon fiber preform of (1);
2) The carbon fiber preform is densified to matrix carbon,
the process for densifying the matrix carbon is chemical vapor deposition: the chemical vapor deposition process conditions are as follows: placing the carbon fiber preform into a deposition furnace, and introducing a carbon-containing gas source (methane and hydrogen 1;
3) Processing the sheet blank into a copying artificial bone blank (comprising a preset hole with the aperture of 1.0 mm) according to an artificial bone defect filling model designed by medical image data CT, wherein the shape is as shown in figure 1;
4) Sequentially depositing a metal layer and a low-temperature carbon layer on the surface of the artificial bone blank;
the metal layer is generated by magnetron sputtering, and the generation conditions are as follows: vacuum degree of 2X 10 -1 Pa; the negative bias voltage of the workpiece is 100V; the Ar flow is 100sccm; the purity of the metal target material Ti is 99wt%, and the power is 2kW; the revolution speed of the material table is 10r/min; the deposition temperature is 280 ℃; the deposition time was 120min.
The low-temperature carbon layer is generated by magnetron sputtering, and the generation conditions are as follows: vacuum degree of 2X 10 -1 Pa; the negative bias voltage of the workpiece is 50V; ar flow is 70sccm; the power of the graphite target is 3kW, and the purity of the graphite target is 99.99wt%; the revolution speed of the material table is 10r/min; the heating temperature is 130 ℃; the deposition time was 200min.
5) Subjecting 4) to high temperature treatment (conditions: the temperature is 1200 ℃; time, 1h; protective atmosphere Ar) to obtain a transition layer containing a ceramic phase;
6) Preparing a deposited pyrolytic carbon coating on the surface of the artificial bone blank body with the ceramic phase formed on the surface;
the pyrolytic carbon coating is generated by chemical vapor deposition, and the generation conditions are as follows:
chemical vapor deposition is carried out, and the generation conditions are as follows: methane is used as a carbon source, and the deposition is carried out for 20 hours at the temperature of 1200 ℃.
The thickness of the ceramic coating of the artificial bone repair material prepared in the embodiment is 8 μm, the thickness of the pyrolytic carbon coating is 10 μm, the elastic modulus is 15GPa, the surface hardness is 7GPa, and the thermal conductivity is 0.8 w/(m.K).
Example 2
1) Multiple layers of carbon fiber cloth (1k, 60g/m) 2 ) And a carbon fiber mesh (40 g/m) 2 ) The cross laminated layer is needled and compounded to the required thickness to obtain the bulk density of 0.4g/cm 3 Is a carbon fiber preform;
2) The carbon fiber preform is densified with matrix carbon, and the process for densifying the matrix carbon is an impregnation-cracking process: the carbon fiber preform is subjected to densification processes such as phenolic resin vacuum pressure impregnation, curing treatment, cracking and the like, and the specific process conditions are as follows: the impregnation pressure is 2.0MPa, and the impregnation time is 6h; the curing temperature is 200 ℃, and the curing time is 20 hours; cracking at 1000 deg.c and normal pressure for 10 hr to obtain porous carbon-base composite material blank with porosity of about 55%;
3) Putting the obtained blank into a high-temperature furnace, heating under the vacuum or protective atmosphere condition for removing impurities, wherein the treatment temperature is 1800 ℃, and the heat preservation time is 5h;
4) Processing the sheet blank into a copying artificial bone blank (comprising a preset hole with the aperture of 2.5 mm) according to an artificial bone defect filling model designed by medical image data CT;
5) Sequentially depositing a metal layer and a low-temperature carbon layer on the surface of the artificial bone blank;
the metal layer is generated by magnetron sputtering, and the generation conditions are as follows: vacuum degree of 2X 10 -1 Pa; the negative bias voltage of the workpiece is 100V; the Ar flow is 100sccm; the target material is metal W, the purity is 99wt%, and the power is 3kW; the revolution speed of the material table is 10r/min; the deposition temperature is 280 ℃; the deposition time was 120min.
The low-temperature carbon layer is generated by plasma enhanced chemical vapor deposition, and the generation conditions are as follows: vacuum degree of 3X 10 - 1 Pa; the negative bias voltage of the workpiece is 80V; ar flow is 60sccm; the power of the ion source is 2kW; the hydrocarbon gas being C 2 H 2 The flow rate is 200sccm; the heating temperature is 220 ℃; the deposition time was 200min.
6) Subjecting 4) to high temperature treatment (conditions: the temperature is 1200 ℃; time, 2h; protective atmosphere Ar) to obtain a transition layer containing a ceramic phase;
7) Preparing a deposited pyrolytic carbon coating on the surface of the artificial bone blank body with the ceramic phase formed on the surface;
the pyrolytic carbon coating is generated by chemical vapor deposition, and the generation conditions are as follows:
chemical vapor deposition is carried out, and the generation conditions are as follows: methane is used as a carbon source, and the deposition is carried out for 20 hours at the temperature of 1200 ℃.
The thickness of the ceramic coating of the artificial bone repair material prepared in this example was 6 μm, the thickness of the pyrolytic carbon coating was 10 μm, the elastic modulus was 12GPa, the surface hardness was 4GPa, and the thermal conductivity was 0.6 w/(m.K).
Example 3
1) Multiple layers of single carbon fiber net (60 g/m) 2 ) Laminating, needling and compounding to the required thickness to obtain the product with the volume density of 0.2g/cm 3 Is a carbon fiber preform;
2) Densifying a carbon fiber preform to obtain matrix carbon, wherein the process for densifying the matrix carbon comprises the following steps of chemical vapor deposition, impregnation-cracking:
the chemical vapor deposition process conditions are as follows: the carbon fiber preform was placed in a deposition furnace, and deposited for 10 hours at a temperature of 1100 ℃ with a carbon-containing gas source (methane and hydrogen 1.
The impregnation-cracking process comprises the densification process processes of phenolic resin vacuum pressurization impregnation, curing treatment, cracking and the like, and the process conditions are as follows: the dipping pressure is 2.0MPa, and the dipping time is 6h; the curing temperature is 200 ℃, and the curing time is 20 hours; cracking at 1000 deg.c and normal pressure for 10 hr to obtain porous carbon-base composite material blank with porosity of about 45%;
3) Processing the sheet blank into a copying artificial bone blank (comprising a preset hole with the aperture of 2.0 mm) according to an artificial bone defect filling model designed by medical image data MRI;
4) Sequentially depositing a metal layer and a low-temperature carbon layer on the surface of the artificial bone blank;
the metal layer is generated by magnetron sputtering, and the generation conditions are as follows: vacuum degree of 2X 10 -1 Pa; the negative bias voltage of the workpiece is 100V; the Ar flow is 100sccm; the target material is metal Zr, the purity is 99.5wt%, and the power is 3kW; the revolution speed of the material table is 10r/min; the deposition temperature is 280 ℃; the deposition time was 120min.
The low-temperature carbon layer is generated by plasma enhanced chemical vapor deposition, and the generation conditions are as follows: vacuum degree of 5X 10 - 1 Pa; the negative bias voltage of the workpiece is 80V; ar flow is 60sccm; the power of the ion source is 2kW; the hydrocarbon gas being C 2 H 2 The flow rate is 200sccm; the heating temperature is 220 ℃; the deposition time was 200min.
5) Subjecting 4) to high temperature treatment (conditions: temperature, 1100 ℃; time, 2h; vacuum) to obtain a transition layer containing a ceramic phase;
6) Preparing a deposited pyrolytic carbon coating on the surface of the artificial bone blank body with the ceramic phase formed on the surface;
the pyrolytic carbon coating is generated by chemical vapor deposition, and the generation conditions are as follows:
chemical vapor deposition is carried out, and the generation conditions are as follows: methane is used as a carbon source, and deposition is carried out for 40h at the temperature of 1200 ℃.
The thickness of the ceramic coating of the artificial bone repair material prepared in this example was 6 μm, the thickness of the pyrolytic carbon coating was 20 μm, the elastic modulus was 12GPa, the surface hardness was 5GPa, and the thermal conductivity was 0.7 w/(m.K).
Comparative example 1
Steps 1) to 5 are the same as in example 1;
6) Preparing a deposited pyrolytic carbon coating on the surface of the artificial bone blank body with the ceramic phase formed on the surface;
the pyrolytic carbon coating is generated by chemical vapor deposition, and the generation conditions are as follows: adopting methane as a carbon source, and depositing at 1200 ℃ for 120h;
the thickness of the ceramic coating of the artificial bone repair material prepared in this example was 8 μm, the thickness of the pyrolytic carbon coating was 12 μm, the elastic modulus was 15GPa, the surface hardness was 2GPa, and the thermal conductivity was 1.5 w/(m.K).
Comparative example 2
Step 1) to step 3) are the same as in example 1;
4) Sequentially depositing a metal layer and a low-temperature carbon layer on the surface of the artificial bone blank;
the metal layer is generated by magnetron sputtering, and the generation conditions are as follows: vacuum degree of 2X 10 -1 Pa; the negative bias voltage of the workpiece is 100V; the Ar flow is 100sccm; the target material is metal Ti, the purity is 99wt%, and the power is 3kW; the revolution speed of the material table is 10r/min; the deposition temperature wei is 280 ℃; the deposition time was 300min.
The low-temperature carbon layer is generated by magnetron sputtering, and the generation conditions are as follows: vacuum degree of 2X 10 -1 Pa; the negative bias voltage of the workpiece is 50V; ar flow is 70sccm; the power of the graphite target is 3kW, and the purity is 99.99wt%; the revolution speed of the material table is 10r/min; the heating temperature is 130 ℃; the deposition time was 500min.
Step 5) is the same as in example 1;
6) Preparing a deposited pyrolytic carbon coating on the surface of the artificial bone blank body with the ceramic phase formed on the surface;
the pyrolytic carbon coating is generated by chemical vapor deposition, and the generation conditions are as follows:
chemical vapor deposition is carried out, and the generation conditions are as follows: adopting methane as a carbon source, and depositing at 1200 ℃ for 120h.
The thickness of the ceramic coating of the artificial bone repair material prepared in this example was 20 μm, the thickness of the pyrolytic carbon coating was 12 μm, the elastic modulus was 15GPa, the surface hardness was 15GPa, and the thermal conductivity was 0.6 w/(m.K).

Claims (5)

1. A carbon-based composite material artificial bone repairing material is characterized in that: a ceramic layer and a pyrolytic carbon layer are sequentially arranged on the surface of the carbon-based porous material;
the carbon-based porous material is a carbon fiber/carbon composite material; the carbon fiber/carbon composite material is formed by a carbon fiber fabric formed by alternately laminating and needling a plurality of layers of carbon fiber cloth and a carbon fiber net or by laminating and needling a plurality of layers of single carbon fiber nets and a carbon substrate inside the carbon fiber fabric; the ceramic layer is formed by at least one of Ti, si, W, cr, ta and Zr and a low-temperature carbon layer at the high temperature of 1000-1500 ℃;
the thickness of the ceramic layer is 3-15 μm;
the thickness of the pyrolytic carbon layer is 5-50 μm;
the carbon-based composite material artificial bone repair material is prepared by the following method: the method comprises the steps of sequentially generating a metal layer on the surface of a carbon-based porous material substrate of the copying artificial bone through magnetron sputtering and generating a low-temperature carbon layer through magnetron sputtering or plasma enhanced chemical vapor deposition, then carrying out high-temperature heat treatment to enable the metal layer and the low-temperature carbon layer to form a ceramic layer, and then carrying out chemical vapor deposition to pyrolyze the carbon layer to obtain the artificial bone.
2. The carbon-based composite material artificial bone repair material according to claim 1, characterized in that: the porosity of the carbon fiber/carbon composite material is 40% -60%.
3. The carbon-based composite material artificial bone repair material according to claim 1, wherein: the metal layer is generated by magnetron sputtering, and the generation conditions are as follows: vacuum degree of 1X 10 -1 Pa ~5×10 -1 Pa; the negative bias of the workpiece is 50V to 200V; ar flow is 20sccm to 200sccm; the purity of the metal target is not lower than 99wt%, and the power is 1kW to 5kW; the revolution speed of the material table is 10 r/min-30 r/min; the deposition temperature is 200-400 ℃; the deposition time is 30min to 300min; the metalThe target material is at least one of Ti, si, W, cr, ta and Zr.
4. The carbon-based composite material artificial bone repair material according to claim 1, wherein:
the low-temperature carbon layer is generated by magnetron sputtering, and the generation conditions are as follows: vacuum degree of 1X 10 -1 Pa~5×10 -1 Pa; negative bias of the workpiece is 10V to 200V; ar flow is 50sccm to 120sccm; the graphite target power is 1kW to 3kW; the purity of the graphite target is not lower than 99.99wt%; the revolution speed of the material table is 10 r/min-30 r/min; the heating temperature is 80-200 ℃; the deposition time is 60-600 min;
alternatively, the first and second electrodes may be,
the low-temperature carbon layer is generated by plasma enhanced chemical vapor deposition, and the generation conditions are as follows: vacuum degree of 1X 10 -1 Pa ~5×10 -1 Pa; negative bias of the workpiece is 10V to 200V; ar flow is 50sccm to 120sccm; the power of an ion source is 0.5kW to 5kW; the flow rate of the hydrocarbon gas is 10sccm to 500sccm; the heating temperature is 80-300 ℃; the deposition time is 60min to 600min.
5. The carbon-based composite material artificial bone repair material according to claim 1, wherein: the pyrolytic carbon layer is generated by chemical vapor deposition under the following conditions: depositing for 10 to 100h at 900 to 1500 ℃ by adopting a gas carbon source.
CN202011037042.4A 2020-09-28 2020-09-28 Carbon-based composite material artificial bone repair material and preparation method thereof Active CN112190761B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011037042.4A CN112190761B (en) 2020-09-28 2020-09-28 Carbon-based composite material artificial bone repair material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011037042.4A CN112190761B (en) 2020-09-28 2020-09-28 Carbon-based composite material artificial bone repair material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112190761A CN112190761A (en) 2021-01-08
CN112190761B true CN112190761B (en) 2022-10-18

Family

ID=74007484

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011037042.4A Active CN112190761B (en) 2020-09-28 2020-09-28 Carbon-based composite material artificial bone repair material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112190761B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114230357B (en) * 2021-12-22 2023-01-31 中国电子科技集团公司第三十八研究所 Preparation method of composite material slot waveguide antenna

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57134154A (en) * 1981-02-12 1982-08-19 Otani Sugirou Carbonacious artificial filler and prosthetic material and production thereof
JP2014047127A (en) * 2012-09-04 2014-03-17 Toyo Tanso Kk Metal-carbon composite material, manufacturing method of metal-carbon composite material, and sliding member
CN107536659B (en) * 2017-08-23 2019-09-17 湖南碳康生物科技有限公司 A kind of integral carbon fibre composite material artificial bone and preparation method thereof
CN107518962B (en) * 2017-08-23 2019-01-08 湖南碳康生物科技有限公司 A kind of carbon fibre composite artificial bone and preparation method thereof

Also Published As

Publication number Publication date
CN112190761A (en) 2021-01-08

Similar Documents

Publication Publication Date Title
CN112190756B (en) Preparation method of carbon fiber composite material profiling artificial bone
US20200188117A1 (en) Carbon fiber composite artificial bone and preparation method thereof
US5217657A (en) Method of making carbon-carbon composites
US7374709B2 (en) Method of making carbon/ceramic matrix composites
US7938992B2 (en) CVI followed by coal tar pitch densification by VPI
CN112190761B (en) Carbon-based composite material artificial bone repair material and preparation method thereof
CN110606762B (en) Carbon fiber composite skull repairing piece and preparation method thereof
CN107536659B (en) A kind of integral carbon fibre composite material artificial bone and preparation method thereof
CN104446666B (en) A kind of restorative procedure of ceramic matric composite thermal damage crackle
CN111908935B (en) Carbon-based composite material bone screw and preparation method thereof
CN112190375B (en) High-bioactivity carbon fiber/carbon composite material C-shaped artificial trachea stent and preparation method thereof
CN111925226B (en) Carbon fiber composite skull patch and preparation method thereof
CN112370569B (en) Carbon fiber composite material artificial rib and preparation method thereof
CN107266103B (en) High density carbon-carbon friction material
CN106967956B (en) A kind of porous hydroxyapatite/nitridation the titanium bioactive coating and purposes of maskable harmful ion release
CN110606746B (en) Skull repairing patch and preparation method thereof
CN111548177A (en) Preparation method of carbon fiber reinforced ceramic matrix composite and pyrolytic carbon interface layer
JPH01264964A (en) Carbon fiber-reinforced composite material having excellent thermal impact resistance and its production
Marković Use of coal tar pitch in carboncarbon composites
CN112206355B (en) Profiling artificial bone and preparation method thereof
JPH04503050A (en) Pyrolytic carbon-containing molded product, its manufacturing method and application
CN213884404U (en) Carbon fiber rope weaved composite bone plate
CN111925227B (en) Carbon fiber composite material artificial trachea stent and preparation method thereof
CN110483048A (en) A kind of graphite heat storage and preparation method thereof
CN213883674U (en) Carbon fiber/carbon composite material T-shaped artificial rib connecting piece

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant